CN113186398B - Fluorine removal system for lithium iron phosphate battery powder and fluorine removal method using same - Google Patents
Fluorine removal system for lithium iron phosphate battery powder and fluorine removal method using same Download PDFInfo
- Publication number
- CN113186398B CN113186398B CN202110224645.3A CN202110224645A CN113186398B CN 113186398 B CN113186398 B CN 113186398B CN 202110224645 A CN202110224645 A CN 202110224645A CN 113186398 B CN113186398 B CN 113186398B
- Authority
- CN
- China
- Prior art keywords
- iron phosphate
- lithium iron
- defluorination
- box body
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/02—Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention provides a fluorine removal system for lithium iron phosphate battery powder and a fluorine removal method using the same. Through a two-stage defluorination process of calcium oxide precipitation defluorination and resin defluorination, fluoride ions in the lithium iron phosphate leaching solution are reduced; the two-stage defluorination process of calcium oxide precipitation defluorination and resin defluorination has the characteristics of low defluorination cost and high efficiency, and is a process which is worthy of popularization and application in production.
Description
Technical Field
The invention relates to the field of battery recovery, in particular to a fluorine removal system for lithium iron phosphate battery powder and a fluorine removal method using the same.
Background
The waste lithium iron phosphate is recycled, a sulfuric acid system oxidation leaching process is generally adopted to extract lithium elements, and in the oxidation leaching process, fluorine elements in electrolyte and a binder can corrode production equipment along with the whole recycling process, and can be brought into lithium products to cause unqualified products, so that effective defluorination equipment needs to be developed aiming at the recycling process of lithium iron phosphate batteries.
Disclosure of Invention
In order to solve the problems, the fluorine removal system for the lithium iron phosphate battery powder and the fluorine removal method using the system have important practical significance.
The purpose of the invention can be realized by the following technical scheme:
lithium iron phosphate battery powder defluorination system, including the box structure that is equipped with the support, box structure left side is equipped with the feed inlet, be equipped with the baffle in the box structure, baffle one side is the pyrolysis zone, and the opposite side is the reaction zone, be equipped with horizontal backup pad on the support, be equipped with the pneumatic cylinder in the horizontal backup pad, be equipped with first diaphragm and second diaphragm in the pyrolysis zone, first diaphragm is located the bottom in pyrolysis zone, the second diaphragm is located the top in pyrolysis zone, connect first diaphragm and second diaphragm after the body of rod of pneumatic cylinder passes recovery bottom half, first diaphragm below is equipped with heating device, be equipped with air inlet and gas outlet on the recovery box front panel, be equipped with the long-pending flitch in the reaction zone, connect the pull rod on the long-flitch, the pull rod passes the box structure and is equipped with the pull rod handle, box structure right side wall is equipped with discharge gate and liquid outlet, intercommunication sedimentation tank on the liquid outlet, the sedimentation tank top is the charge door, the sedimentation tank below is equipped with the discharging pipe, the discharging pipe top is equipped with and crosses the filter plate, be equipped with the valve on the discharging pipe, discharging pipe bottom communicates resin defluorination box.
The further technology of the invention is as follows:
preferably, the left side of the box body structure is further provided with a material pushing port, a material pushing plate is arranged in the material pushing port, and a vertical notch is formed in the middle of the material pushing plate.
Preferably, the reaction zone is filled with sulfuric acid and hydrogen peroxide.
Preferably, the inside exchange column that is of resin defluorination box, establish the packing resin in the exchange column, be equipped with the water inlet on the discharging pipe, the inlet tube is connected to the water inlet, the water inlet is located the valve below.
Preferably, the method for removing fluorine from lithium iron phosphate battery powder comprises the steps that a pyrolysis area is formed by a second transverse plate, a partition plate and a box body structure, lithium battery powder enters the pyrolysis area from a feeding hole, is pyrolyzed under the protection of nitrogen, so that electrolyte and a binder in the battery powder are decomposed, then the lithium battery powder enters a reaction area, reacts under the action of sulfuric acid and hydrogen peroxide, and fluoride ions can be removed in a calcium fluoride precipitation mode through solid-liquid separation to obtain lithium iron phosphate leachate;
taking lithium iron phosphate leachate for a precipitation method defluorination experiment, feeding the lithium iron phosphate leachate into a sedimentation tank through a liquid outlet, and adding calcium oxide powder into the lithium iron phosphate leachate for reaction;
and opening a valve after reaction, feeding the lithium iron phosphate leaching solution into an exchange column through a discharge pipe, taking 2 exchange columns, dividing the exchange columns into a head column and a tail column, and performing regeneration and washing procedures, and then feeding, adsorbing and defluorinating.
Preferably, the regeneration and washing procedure comprises
(1) Primary water washing: the water inlet volume is 40mL, and the water inlet flow is 2BV/h;
(2) alkali washing: the alkali liquor contains 4 percent of sodium hydroxide, the alkali feeding volume is 40mL, and the alkali feeding flow is 1BV/h;
(3) and (3) secondary water washing: the water inlet volume is 40mL, and the water inlet flow is 2BV/h;
(4) acid washing: the acid solution contains 3 percent of sulfuric acid, the volume of the acid is 40mL, and the flow rate of the alkali is 1BV/h;
(5) and (3) washing for the third time: the water inlet volume is 40mL, and the water inlet flow is 2BV/h;
(6) feeding: the feed liquid is lithium iron phosphate leaching liquid.
The invention has the beneficial effects that: through a two-stage defluorination process of calcium oxide precipitation defluorination and resin defluorination, fluoride ions in the lithium iron phosphate leachate are reduced; the two-stage defluorination process of defluorination by calcium oxide precipitation and resin defluorination has the characteristics of low defluorination cost and high efficiency, and is a process which is worthy of popularization and application in production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic sectional elevation view of the structure of the present invention;
FIG. 2 is a schematic view of the push plate structure of FIG. 1;
FIG. 3 is a table of experimental data of the distribution rule of fluorine ions;
FIG. 4 is a table of resin selection data;
FIG. 5 shows the saturated adsorption amount data of the 3# resin obtained by 10 regenerations.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "vertical", "upper", "lower", "horizontal", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, which are only for convenience of description of the present invention and simplification of description, but do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, "first," "second," "third," and "fourth" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be further noted that, unless otherwise specifically stated or limited, the terms "disposed," "mounted," "connected," and "connected" are to be construed broadly and can be, for example, fixedly connected, detachably connected, integrally connected, mechanically connected, electrically connected, directly connected, connected through an intermediate medium, or connected through two elements. The specific meanings of the above terms in the present invention can be understood according to specific situations by those of ordinary skill in the art.
As shown in fig. 1-2, lithium iron phosphate powder defluorination system, including the box structure 3 that is equipped with support 1, box structure left side is equipped with feed inlet 4, be equipped with baffle 11 in the box structure 3, baffle 11 one side is pyrolysis district 12, and the opposite side is reaction zone 13, be equipped with horizontal backup pad 14 on the support 1, be equipped with pneumatic cylinder 15 on the horizontal backup pad 14, be equipped with first diaphragm 16 and second diaphragm 17 in the pyrolysis district 12, first diaphragm 16 is located the bottom of pyrolysis district 12, second diaphragm 17 is located the top of pyrolysis district 12, the body of rod of pneumatic cylinder 15 passes and connects first diaphragm 16 and second diaphragm 17 after retrieving 2 bottoms of box, first diaphragm 16 below is equipped with heating device 20, be equipped with air inlet and discharging pipe on retrieving 2 front panels of box, be equipped with flitch 21 in the reaction zone 13, connect pull rod 22 on the flitch 21, pull rod 22 passes box structure 3 and is equipped with pull rod 22 handle 23, the right side wall of box structure 3 is equipped with discharge gate 24 and liquid outlet 5, communicate sedimentation tank 6 on the sedimentation tank, the sedimentation tank top is equipped with the charge door 7, is equipped with filter plate bottom, filter plate 8 on the filter plate bottom, be equipped with the resin removal tank 10 on the box.
The box structure left side still is equipped with pushes away material mouth 2, pushes away and is equipped with scraping wings 25 in the material mouth, be equipped with vertical notch 26 in the middle of the scraping wings.
And the reaction zone is filled with sulfuric acid and hydrogen peroxide.
The inside exchange column that is of resin defluorination box, establish the packing resin in the exchange column, be equipped with water inlet 27 on the discharging pipe, the inlet tube is connected to the water inlet, the water inlet is located the valve below.
The lithium battery powder enters the pyrolysis zone from the feeding hole, is pyrolyzed under the protection of nitrogen to decompose electrolyte and binder in the battery powder, then enters the reaction zone, reacts under the action of sulfuric acid and hydrogen peroxide, and fluoride ions can be removed in a calcium fluoride precipitation mode through solid-liquid separation to obtain lithium iron phosphate leachate;
taking the lithium iron phosphate leachate for a defluorination experiment by a precipitation method, feeding the lithium iron phosphate leachate into a sedimentation tank through a liquid outlet, and adding calcium oxide powder into the lithium iron phosphate leachate for reaction;
and opening a valve after reaction, feeding the lithium iron phosphate leaching solution into an exchange column through a discharge pipe, taking 2 exchange columns, dividing the exchange columns into a head column and a tail column, and performing regeneration and washing procedures, and then feeding, adsorbing and defluorinating.
Preferably, the regeneration and washing procedure comprises
Primary water washing: the water inlet volume is 40mL, and the water inlet flow is 2BV/h;
alkali washing: the alkali liquor contains 4 percent of sodium hydroxide, the alkali feeding volume is 40mL, and the alkali feeding flow is 1BV/h;
and (3) secondary water washing: the volume of inlet water is 40mL, and the flow rate of inlet water is 2BV/h;
acid washing: the acid solution contains 3 percent of sulfuric acid, the acid inlet volume is 40mL, and the alkali inlet flow is 1BV/h;
and (3) washing for the third time: the volume of inlet water is 40mL, and the flow rate of inlet water is 2BV/h;
feeding: the feed liquid is lithium iron phosphate leachate.
As shown in fig. 3 to 5, the research experiment of the removal process of fluoride ions in the lithium iron phosphate leaching solution of the present invention:
the distribution rule of fluorine ions in the leaching process of lithium iron phosphate battery powder shows that the content of F in lithium iron phosphate leachate reaches 800mg/L, the lithium iron phosphate leachate belongs to a high-concentration fluorine-containing solution, and according to the characteristics of a chemical fluorine removal process and a physical fluorine removal process, a distributed fluorine removal mode is adopted in the experiment, firstly, the fluorine ions are reduced to be below 100mg/L by a chemical precipitation method, and secondly, deep fluorine removal is carried out by a resin adsorption method.
Precipitation defluorination
And repeating the experiment to obtain a lithium iron phosphate leachate, adding calcium oxide powder into the lithium iron phosphate leachate to perform a precipitation reaction, so that fluoride ions in the lithium iron phosphate leachate are precipitated in the form of calcium fluoride which is difficult to dissolve, thereby removing most of the fluoride ions in the lithium iron phosphate leachate and achieving the purpose of reducing the fluoride ions in the lithium iron phosphate leachate.
0.5g of calcium oxide powder is added into 100g of fluorine-containing 800mg/L lithium iron phosphate leachate, the reaction time is respectively controlled to be 2h,4h and 8h, after solids are filtered out, the corresponding F content in the filtrate is 135mg/L,131mg/L and 129mg/L, and the Ca < 2+ > content in the filtrate is 5mg/L,3mg/L and 3mg/L respectively. The addition amount of calcium oxide is 2 times of the stoichiometric ratio of F in the solution, and as can be seen from the content of Ca < 2+ > in the filtrate, the excessive calcium oxide is not continuously dissolved, mainly because CaF2 is formed on the surface of calcium oxide powder, so that the calcium oxide cannot be continuously dissolved.
And (2) controlling the reaction time to be 2h for 100g of fluorine-containing 800mg/L lithium iron phosphate leachate, respectively adding 0.5g,1g and 2g of calcium oxide powder, filtering out solids, wherein the corresponding F contents in the filtrate are 135mg/L,48mg/L and 24mg/L, and the Ca & lt 2+ & gt contents in the filtrate are 5mg/L,21mg/L and 72mg/L respectively. As can be seen from the content of Ca2+ in the filtrate, as the amount of calcium oxide powder added increases, the F content in the solution decreases and the Ca2+ content increases. It can be seen that, with the increase of calcium oxide powder, a complete and compact CaF2 protective layer cannot be formed on the surface of calcium oxide, resulting in continuous dissolution of excessive calcium oxide.
Adding 1g of calcium oxide powder into 100g of fluorine-containing 800mg/L lithium iron phosphate leachate, respectively controlling the reaction time to be 2h,4h and 8h, filtering out solids, wherein the corresponding F content in the filtrate is 48mg/L,33mg/L and 13mg/L, and the Ca < 2+ > content in the filtrate is 21mg/L,18mg/L and 22mg/L. The amount of calcium oxide added was about 4 times the stoichiometric ratio of F ions in the solution, and as can be seen from the F and Ca2+ content of the filtrate, the F content slowly decreased while the Ca2+ content tended to stabilize. Under the principle that impurity ions are introduced into the lithium iron phosphate leaching solution as little as possible, the addition amount of calcium oxide is 1g, and the reaction time is 2-4 h, so that the method is a relatively excellent chemical defluorination process parameter.
Defluorination of resins
According to different resin principles, the method selects three defluorination resins with different mechanisms, including anion exchange resin (1 # resin), aluminum-based composite resin (2 # resin) and zirconium-based composite resin (3 # resin), then uses the method to perform a resin model selection experiment on the defluorinated lithium iron phosphate leachate (with the F content of 48 mg/L) precipitated by a calcium method, and tests the saturated adsorption capacity of each resin, the F content of the material liquid after defluorination of the resin and the impurity introduction amount.
The saturated adsorption capacity of the resin 1, the saturated adsorption capacity of the resin 2 and the saturated adsorption capacity of the resin 3 are respectively 0.3g/L,2.6g/L and 2.8g/L, wherein the aluminum-based composite resin (the resin 2) and the zirconium-based composite resin (the resin 3) both have higher saturated adsorption capacity, but the capacity of the anion exchange resin (the resin 1) is lower; the content of fluorine ions in the liquid after the feed liquid is subjected to fluorine removal can be seen, the aluminum-based composite resin (2 # resin) and the zirconium-based composite resin (3 # resin) can realize deep fluorine removal of the lithium iron phosphate leachate, and the content of the fluorine ions in the lithium iron phosphate leachate can be reduced to be below 1 mg/L; as can be seen from the impurity ion content of the liquid after the fluoride removal of the feed liquid, the aluminum matrix composite resin (2 # resin) can introduce a large amount of impurities into the feed liquid; after the zirconium-based resin (3 # resin) is regenerated for 10 times, the saturated adsorption capacity is not obviously attenuated, and the regeneration performance is good. The zirconium-based resin (3 # resin) is the best resin of the three kinds of fluorine removal resins by comprehensively considering the fluorine removal effect, the introduction amount of impurities in the feed liquid and the reproducibility.
And (4) conclusion:
1) By analyzing the distribution rule of F in the recycling process of lithium iron phosphate systematically, the content of F in the original lithium iron phosphate battery powder is up to 2.5 percent by weight, about 86 percent of F volatilizes out in a gas form in the pyrolysis process, and 14 percent of F remains in the pyrolyzed lithium iron phosphate battery powder. During the oxidation leaching, about 60% of F remained in the wet slag, 40% of F finally entered into the lithium iron phosphate leachate, and as can be seen from the F content of the lithium iron phosphate leachate in the table, the F concentration of the lithium iron phosphate leachate was as high as 0.08%.
2) The calcium oxide powder can effectively reduce F in the lithium iron phosphate leaching solution to be below 50mg/L, and Ca < 2+ > introduced into the feed liquid is not more than 25mg/L. Under normal temperature, for 100g of feed liquid containing 800mg/L of fluorine, the addition amount of calcium oxide is 1g, and the chemical defluorination process parameter is relatively excellent under the condition that the reaction time is 2-4 h.
3) The type selection of the deep fluorine removal resin is considered, the anion exchange resin (1 # resin), the aluminum-based composite resin (2 # resin) and the zirconium-based composite resin (3 # resin) have the worst adsorption effect on the fluorine ions in the lithium iron phosphate leachate, and the aluminum-based composite resin and the zirconium-based composite resin can reduce the fluorine ions in the lithium iron phosphate leachate to below 1mg/L and have high saturated adsorption capacity; however, the aluminum-based resin can introduce aluminum element of up to 100mg/L into the feed liquid, and seriously pollute the feed liquid. The regeneration test of the zirconium-based resin shows that the saturated adsorption capacity of the zirconium-based resin is not substantially attenuated. Therefore, the zirconium-based composite resin is the resin which is most suitable for deeply removing F in the lithium iron phosphate leaching solution in the three resins.
4) The two-stage defluorination process of calcium oxide precipitation defluorination and zirconium-based resin defluorination proves that F in the lithium iron phosphate leaching solution can be reduced to 0.4mg/L. The two-stage defluorination process of defluorination by calcium oxide precipitation and zirconium-based resin has the characteristics of low defluorination cost and high efficiency, and is a process which is worthy of popularization and application in production.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, and such changes and modifications are within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (3)
1. Lithium iron phosphate battery powder defluorination system, its characterized in that: the box body structure comprises a box body structure provided with a support, wherein a feed inlet is formed in the left side of the box body structure, a partition plate is arranged in the box body structure, one side of the partition plate is a pyrolysis region, the other side of the partition plate is a reaction region, a transverse support plate is arranged on the support, a hydraulic cylinder is arranged on the transverse support plate, a first transverse plate and a second transverse plate are arranged in the pyrolysis region, the first transverse plate is located at the bottom of the pyrolysis region, the second transverse plate is located at the top of the pyrolysis region, a rod body of the hydraulic cylinder penetrates through the bottom of a recovery box body and then is connected with the first transverse plate and the second transverse plate, a heating device is arranged below the first transverse plate, an air inlet and an air outlet are formed in the front panel of the recovery box body, a material accumulation plate is arranged in the reaction region, a pull rod is connected to the material accumulation plate, the pull rod penetrates through the box body structure and is provided with a pull rod handle, a discharge outlet and a liquid outlet are formed in the right side wall of the box body structure, a sedimentation tank is communicated to the liquid outlet, a feed inlet is formed above the sedimentation tank, a discharge pipe is arranged below the sedimentation tank, a filter screen plate is arranged at the top end of the sedimentation tank, a filter screen plate is arranged on the discharge pipe, and the discharge pipe is arranged on the discharge pipe, and the bottom of the discharge pipe is communicated with a resin defluorination box body;
an exchange column is arranged inside the resin defluorination box body, filled resin is arranged in the exchange column, a water inlet is arranged on the discharge pipe and is connected with a water inlet pipe, and the water inlet is positioned below the valve;
the defluorination method utilizing the defluorination system of the lithium iron phosphate battery powder comprises the steps that a pyrolysis area is formed by a second transverse plate, a partition plate and a box body structure, the lithium battery powder enters the pyrolysis area from a feeding hole, is pyrolyzed under the protection of nitrogen, so that electrolyte and a binder in the battery powder are decomposed, then the lithium battery powder enters a reaction area, reacts under the action of sulfuric acid and hydrogen peroxide, and fluoride ions can be removed in a calcium fluoride precipitation mode through solid-liquid separation to obtain lithium iron phosphate leachate;
taking the lithium iron phosphate leachate for a defluorination experiment by a precipitation method, feeding the lithium iron phosphate leachate into a sedimentation tank through a liquid outlet, and adding calcium oxide powder into the lithium iron phosphate leachate for reaction;
opening a valve after reaction, feeding lithium iron phosphate leachate into an exchange column through a discharge pipe, taking 2 exchange columns to be divided into a head column and a tail column, and performing regeneration and washing procedures on the two columns to perform feeding, adsorption and defluorination;
the regeneration and washing procedures include
(1) Primary water washing: the volume of inlet water is 40mL, and the flow rate of inlet water is 2BV/h;
(2) alkali washing: the alkali liquor contains 4 percent of sodium hydroxide, the alkali feeding volume is 40mL, and the alkali feeding flow is 1BV/h;
(3) and (3) secondary water washing: the volume of inlet water is 40mL, and the flow rate of inlet water is 2BV/h;
(4) acid washing: the acid solution contains 3 percent of sulfuric acid, the volume of the acid is 40mL, and the flow rate of the alkali is 1BV/h;
(5) and (3) washing for the third time: the volume of inlet water is 40mL, and the flow rate of inlet water is 2BV/h;
(6) feeding: the feed liquid is lithium iron phosphate leachate.
2. The lithium iron phosphate battery powder fluorine removal system as set forth in claim 1, wherein: the box structure left side still is equipped with pushes away the material mouth, pushes away and is equipped with the scraping wings in the material mouth, be equipped with vertical notch in the middle of the scraping wings.
3. The lithium iron phosphate battery powder defluorination system as set forth in claim 1 wherein: and the reaction zone is filled with sulfuric acid and hydrogen peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110224645.3A CN113186398B (en) | 2021-03-01 | 2021-03-01 | Fluorine removal system for lithium iron phosphate battery powder and fluorine removal method using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110224645.3A CN113186398B (en) | 2021-03-01 | 2021-03-01 | Fluorine removal system for lithium iron phosphate battery powder and fluorine removal method using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113186398A CN113186398A (en) | 2021-07-30 |
| CN113186398B true CN113186398B (en) | 2023-01-13 |
Family
ID=76973037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110224645.3A Active CN113186398B (en) | 2021-03-01 | 2021-03-01 | Fluorine removal system for lithium iron phosphate battery powder and fluorine removal method using same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113186398B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115072751B (en) * | 2022-08-23 | 2022-11-01 | 矿冶科技集团有限公司 | Method for preparing low-fluorine lithium carbonate by recycling lithium iron phosphate battery |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6612506B2 (en) * | 2015-02-14 | 2019-11-27 | 三菱マテリアル株式会社 | Disposal of used lithium ion batteries |
| CN107196004B (en) * | 2017-05-13 | 2019-07-19 | 合肥国轩高科动力能源有限公司 | A method of recycling valuable metal from applying waste lithium ionic power battery |
| CN109207730B (en) * | 2018-09-19 | 2020-03-10 | 中国科学院青海盐湖研究所 | Method and system for recovering lithium from waste lithium iron phosphate batteries |
| CN110590012B (en) * | 2019-09-12 | 2020-09-22 | 南京大学 | Resource utilization method of deep defluorination resin desorption solution |
| CN110994062A (en) * | 2019-11-27 | 2020-04-10 | 湖南邦普循环科技有限公司 | Recovery method for removing fluorine at front section of waste lithium ion battery |
| CN112079478A (en) * | 2020-08-27 | 2020-12-15 | 中伟新材料股份有限公司 | Method for removing fluorine and heavy metal from sulfate treatment liquid |
| CN112267023B (en) * | 2020-09-25 | 2022-07-08 | 衢州华友钴新材料有限公司 | Two-stage defluorination method for fluorine-containing material |
-
2021
- 2021-03-01 CN CN202110224645.3A patent/CN113186398B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113186398A (en) | 2021-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4242185A (en) | Process and apparatus for controlling impurities and pollution from membrane chlor-alkali cells | |
| CN110527836A (en) | A kind of method that ion-exchange recycles valuable metal in waste and old nickel cobalt manganese lithium ion battery | |
| CN113443640B (en) | Method for preparing battery-grade lithium carbonate and battery-grade iron phosphate by using waste positive and negative electrode powder of lithium iron phosphate battery | |
| CN113186398B (en) | Fluorine removal system for lithium iron phosphate battery powder and fluorine removal method using same | |
| CN113073194B (en) | Defluorination process for recycling waste lithium batteries | |
| CN106957124A (en) | A kind of tertiary cathode material produces the processing method and processing system of waste water | |
| CN106698352A (en) | Method and device for preparing high-purity fluorine gas or high-purity fluorine-containing mixed gas | |
| US4144145A (en) | Process for recovery of reusable chromic acid from the waste chromic acid solution containing impurities | |
| CN106575807A (en) | Method for regenerating alkaline solutions | |
| CN205953515U (en) | Regeneration system of peace and quiet spent acid of acetylene | |
| AU638306B2 (en) | Process of reclaiming battery acid from lead acid batteries | |
| CN114852966A (en) | Method and device for removing HF in fluorine gas | |
| US2719822A (en) | Production of chlorine from hydrogen chloride | |
| CN106495356A (en) | The processing method and system of steel industry nitric hydrofluoric acid mixed acid pickle liquor | |
| US11293077B2 (en) | Method for recovering scandium from red mud left from alumina production | |
| CN109055748A (en) | Defluorination chlorine agent and preparation method thereof and method for defluorination chlorine using same | |
| CN206751588U (en) | A kind of processing system of tertiary cathode material production waste water | |
| CN211689249U (en) | Device for dewatering anhydrous hydrogen fluoride | |
| CN214495731U (en) | Device for removing HF in fluorine gas | |
| CN218785070U (en) | Electrolytic aluminum waste carbon electrode wet separation device and resource utilization system | |
| JPH029703A (en) | Method for recovering sulfur | |
| CN219314591U (en) | Reaction absorption tower device for efficiently separating lithium element in waste lithium ion battery | |
| CN215161246U (en) | Integrated phosphorus recovery fuel cell device | |
| CN220265852U (en) | External overflow acid etching solution copper extraction regeneration electrolytic tank | |
| CN214399825U (en) | Deoxidization device for reagent sulfuric acid production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 236500 No. 5, South Side of Huaxin Avenue, Tianying Industrial Park, Jieshou City, Fuyang City, Anhui Province Patentee after: ANHUI NANDU HUABO NEW MATERIAL TECHNOLOGY Co.,Ltd. Patentee after: Huayu New Energy Technology Co.,Ltd. Address before: 236500 No. 5, South Side of Huaxin Avenue, Tianying Industrial Park, Jieshou City, Fuyang City, Anhui Province Patentee before: ANHUI NANDU HUABO NEW MATERIAL TECHNOLOGY Co.,Ltd. Patentee before: JIESHOU NANDU HUAYU POWER SOURCE Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230522 Address after: 236500 No. 5, South Side of Huaxin Avenue, Tianying Industrial Park, Jieshou City, Fuyang City, Anhui Province Patentee after: ANHUI NANDU HUABO NEW MATERIAL TECHNOLOGY Co.,Ltd. Address before: 236500 No. 5, South Side of Huaxin Avenue, Tianying Industrial Park, Jieshou City, Fuyang City, Anhui Province Patentee before: ANHUI NANDU HUABO NEW MATERIAL TECHNOLOGY Co.,Ltd. Patentee before: Huayu New Energy Technology Co.,Ltd. |